Process of producing active material and electrodes for storage batteries and products thereof.



PA'TENTED SEPT. 8, 1903 o. P. Pnmcfi'm PROCESS or PRODUGING ACTIVEMATERIAL AND ELECTRODES FORY STORAGE BATTERIES AND PRODUGTS THEREOF;

APPLIOATION FILED JAN. 7, 1903.

no 110mm.

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ale. 738,313.

UNITED STATES Patented September 8, 1903.

PATENT OFFICE.

OLIVER P. FRITCHLE, OF DENVER, COLORADO.

PROCESS OF PRODUCING ACTIVE MATERIAL AND ELECTRODES FOR STORAGEBATTERIES AND 1 PRODUCTS THEREOF.

SPECIFICATION forming part of Letters Patent No. 738,313, datedSeptember 8, 1903. Application filed January-'7, 1903. Serial No.138,167. (No specimens.)

T0 coZZ whom, it may concern.-

Be it known that I, OLIVER P. FRITCHLE, a citizen of the United States,residing at Denver, in the county of Arapahoe and State of Colorado,have invented certain new and useful Improvements in Processes of Producing Active Material and Electrodes for Lead Storage Batteries andProducts Thereof, of which the following is a specification.

This invention relates to the production of a crystallinenon-disintegrating active material of the utmost electrical conductivityand molecular porosity which will allow the freest possible diifusion ofthe electrolyte on charge and discharge. The new active material mayeither be compressed into a self-supporting electrode or may be carriedby a suitable support or grid.

The invention is based on the discovery that finely-divided lead,especially when pro; duced by spraying molten lead by means of a blast,obtains a peculiar cohesive'property as if in a molten state whensubjected to a hot dilute solution of hydrochloric acid and may beWelded together into a rigid but highly-porous mass by subjecting it tolight pressure. The treatment with acid causes a slight evolution ofgas, which prevents the particles of lead from settling into a densecompact mass.

The process may be carried out by theuse of any suitable apparatus.which has been employed with advantage is shown in the accompanyingdrawings, in which- Figure 1 is a transverse vertical section of theentire apparatus. Fig. 2 is a perspective view of a device for holdingthe. finely-divided lead and showering it evenlyinto the An apparatusit. A slide 3 is arranged to move in contact with the lower surface ofthe plate and is supported by rabbeted parallel guide-strips A, securedbeneath the edges of the plate. A vessel 5, which may be a shallowporcelainlined pan, contains a body of dilute hydrochloric acid 6,preferably a fiveper-cent. aqueous solution. Beneath the pan is a gasheater 7, by which the acid solution is brought to a high temperature. Areceiver 8 is supported within the pan at some distance above its bottomand directly beneath the showerplate 11 to receive the treated lead. Astrip 12 closes the slot.

In employing this apparatus to carry out the process the receiver 8,containing the grid 11, is placed in the pan 5, and the acid solution isheated to a high temperature, preferably to its boiling-point. Theapertures in plate 1 are filled with the granulated lead previouslysieved to a size between sixty and one hundred mesh, the slide beingclosed, and

the device'is placed directly above the receiver 8, as shown in Fig. 1.The slide is now slowly withdrawn, and the lead falls through thehotacid solution into the receiver and onto the grid 11. The action ofthe acid solution on the granulated lead quickly causes it to becomecoherent, as if in a molten state, and the treated mass will occupyabout four times the original volume ofthe lead. The lead is nowcompressed to about twice its original volume, preferablywhile it isstill within the hot solution. It is important that the treated leadshould be compressed without delay, as its property of welding is soondestroyed by the continued action of the acid. The pressure required iscomparatively slight,

depending upon the required porosity of the mass, and may be effected bya hand-press with screw-and-toggle mechanism. The bottom of the receiveris now detached, and the grid, with the compressed active material onone of its faces, is pushed out and again inserted with the coating ofactive material below. The bottom is replaced, and the other face of thegrid is provided with a coating of active material by repeating thedescribed operations.

While the use of a conducting or non-conducting grid or support is oftendesirable, this element is not essential. The gran ulated lead afterpassing through the acid may be received directly on the bottom of anysuitable vessel and compressed into a highly-porous and self-supportingelectrode of sufficient rigidity for practical use. While the process ispreferably carried out by the use'of the described acid solution, asolution of any other acid, salt, orlcompound which will yield chlorinto the lead may be substituted, or chlorin-water or chlorin itself maybe employed. The use of lead which has been granulated by a blast ispreferable, as the shreds and filaments interlace when the treated massis compressed, giving the body greater tirmness and rigidity. I obtainby my process an electrode possessing all the good qualities of a Plantplate with the high capacity of a Faure plate. a

Heretofore most attempts at producing porous coherent active material ormaterial to become active for storage batteries havebeen by combiningthe lead or compounds of lead with some foreign element and thendissolving out the foreign element after the electrode had been shaped,leaving the mass in a semi-adherentstate easily disintegrated bytheaction of the current on charge and discharge.

A few attempts have been made to weld the particles of lead together bycollecting them unsized when in the molten or seinimolten state; but theforming of blow-holes throughout the mass cannot be avoided, while in mymethod it is'apparent that not a single particle of the lead can be shutoff from the action of the electrolyte from the fact that each particleis surrounded by gas or liquid from the beginning, and this mustpartially escape from the interstices of the mass upon applying thepressure in welding.

I am also aware that electrolytically-deposited crystals of lead havebeen compressed into a coherent mass for storage-battery electrodes; butthe crystals of deposited lead are so minute, almost molecular, thatafter comtrolyte and the Washing out of any detached particles ofsulfate.

The electrode produced bythis process may be formed by any suitablemethod.

The apparatus shown and described herein is claimed in myapplication,-Serial No. 138,168,

of even date herewith.

I claim- 1. The process of producing active material for lead storagebatteries, which consists in subjecting finely-divided lead to theaction of chlorin and heat, as set forth.

2. The process of producing active material for lead storage batteries,which consists in subjecting finely-divided lead to the action of heatand a compound which will yield chlorin, as set forth.

3. The process of producing active material for lead storage batteries,which consists in subjecting finely-divided lead to the action ofhydrochloric acid and heat, as set forth.

4. The process of producing active material for lead storage batteries,which consists in subjecting finely-divided lead to the action of dilutehydrochloric acid and heat, as set forth.

' 5. The process of producing active material for lead storagebatteries, which consists in showering finely-divided lead intoahot,dilute solution of hydrochloric acid, as set forth.

6. The process of producing active material for lead storage batteries,which consists in subjecting finely-divided lead to the action ofchlorin and heat, and then compressing the treated lead into a coherent,porous mass, as set forth.

7. The process of producing active material for lead storage batteries,which consists in subjecting finely-divided lead to the action ofhydrochloric acid and heat, and then compressing the treated lead into acoherent, porous mass, as set forth.-

8. The process of producing active material for lead storage batteries,which consists in showering finely-divided lead into a hot, di: lutesolution of hydrochloric acid, and then compressing the treated leadinto a coherent, porous mass, as set forth.

9. The process of producing active material for lead storage batteries,which consists in spraying molten lead by a blast, subjecting thefinely-divided lead to the action of hydrochloric acid and heat, andcompressing the treated lead into a coherent, porous mass, as set forth.

10. The process of producing active material for lead storage batteries,which consists in spraying molten lead by a blast, showering thefinely-divided lead into a hot, dilute solution of hydrochloric acid,and then compressing the treated lead into a coherent, porous mass, asset forth.

11. The process of producing electrodes for lead storage batteries,which consists in ap: plying granulated lead to a support and subjectingit to the action of chlorin and heat, and then compressing the treatedlead into a coherent, porous mass, as set forth.

12. The process of producing electrodes for lead storage batteries,which consists in applying granulated lead to a support and subjectingit to the action of hydrochloric acid and heat, and then compressing thetreated lead intoa coherent, porous mass, as set forth.

13. The process of producing electrodes for lead storage batteries,which consists in show ering granulated lead through a hot, dilutesolution of hydrochloric acid onto a support,

and then compressing the treated lead into a coherent, porous mass, asset forth.

14.. Active material for lead storage batteries, produced by subjectingfinely-divided lead to the action of chlorin and heat, as set forth.

15. Active material for lead storage batteries, produced by subjectingfinely-divided lead to the action of hydrochloric acid and heat, as setforth.

16. Active material for lead storage batteries, produced by showeringfinely-divided lead through a hot, dilute solution of hydrochloric acid,as set forth.

17. Active material for lead storage batteries, produced by subjectinggranulated lead to the action of chlorin and heat and then compressingthe treated lead into a coherent, porous mass, as set forth.

18. Active material for lead storage batteries, produced by subjectinggranulated lead to the action of hydrochloric acid and heat and thencompressing the treated lead into a coherent, porous mass, as set forth.

19. Active material for lead storage bat,- teries, produced by showeringgranulated lead through a hot, dilute solution of hydrochloric acid andthen compressing the treated lead into a coherent, porous mass, as setforth.

20. An electrode for lead storage batteries, comprising a support, andactive material produced by subjecting granulated lead to the action ofchlorin and heat and then compressing the treated lead into a coherent,porous mass, as set forth.

21. An electrode for lead storage batteries, comprising a support, andactive material produced by subjecting granulated lead to the action ofhydrochloric acid and heat and then compressing the treated lead into acoherent, porous mass, as set forth.

22. An electrode for lead storage batteries, produced by showering grannlated lead through a hot, dilute solution of hydrochloric acid onto asupport and then compressing the treated lead into a coherent, porousmass, as set forth.

In testimony whereof I affix my signature in presence of two witnesses.

OLIVER P. FRITGIILE. v Witnesses:

W. H. GOETZMAN, SARAH STINSON.

